CN104021842A - Graphene composite copper thick film conductive slurry and preparation method thereof - Google Patents
Graphene composite copper thick film conductive slurry and preparation method thereof Download PDFInfo
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Abstract
The invention discloses graphene composite copper thick film conductive slurry. The graphene composite copper thick film conductive slurry comprises the following components in percentage by mass: 60%-80% of conductive phase, 0.5%-5% of glass phase, 15%-39.5% of organic carrier, totaling 100%. The preparation method comprises the steps of mixing the components, heating to 35-40 DEG C, and uniformly stirring. According to the graphene composite copper thick film conductive slurry disclosed by the invention, by adding graphene with an excellent conductive property, the conductive property of the slurry is improved; by bismuth oxide low-melting glass, the conductive thick film slurry has excellent electrical properties and adhesion force even when being sintered at a low temperature. The slurry has the advantages of good conductivity and small printing thickness, can be effectively applied to production of a conductive material for various products, has the advantages of simple preparation process, convenience in operation, good conductivity, uniform distribution of particle sizes and easiness in coating, and is suitable for mass production of enterprises.
Description
Technical field
The invention belongs to electric slurry technical field, the present invention relates to a kind of Graphene complex copper thick film conductor paste, the invention still further relates to the preparation method of this electrocondution slurry.
Background technology
In recent years, electric slurry has been widely used in the every field of electron trade, along with the fast development of electronic industry, the demand of electric slurry is also increased gradually.Use traditionally the electrocondution slurry of the noble silver composition of electric conductivity excellence, but silver is expensive, be difficult to meet requirement cheaply, therefore people attempt utilizing the material copper etc. of lower cost to replace silver, but due to the high resistance after its suboxides stability and sintering, make to exist some problems in preparing slurry process, therefore especially low sintering its electric conductivity of electric slurry is often affected, in the urgent need to a kind of cheap electrocondution slurry still when the low-temperature sintering with excellent electrical property.
Along with electronic component device day by day become miniaturization, microminiaturization, need to obtain with less material high performance product, therefore to make the thick membrane electrode traditionally with tens of micron thickness become more thinner, this electrocondution slurry that print thickness is little with regard to a kind of electric conductivity of needs is fabulous.
Graphene is a kind of new material of the individual layer laminated structure consisting of carbon atom, is known thin, the hardest nano material in the world.Graphene only has the thickness of a carbon atom, and structure is highly stable, and the connection between its inner carbon atom is very pliable and tough, when applying external force in Graphene, carbon atom face meeting flexural deformation, makes carbon atom needn't rearrange to adapt to external force, thereby keeps Stability Analysis of Structures.This stable crystal structure makes Graphene have excellent thermal conductivity, conductive coefficient is up to 5300W/mK, higher than carbon nano-tube and diamond, under normal temperature, its electron mobility surpasses 15000cm2/Vs, the movement velocity of electronics has reached 1/300 of the light velocity, ratio nano carbon pipe or silicon wafer height again, and resistivity only approximately 10
-6Ω cm, lower than Jin Heyin, be the material of resistivity minimum in the world.Therefore because its resistivity is extremely low, the speed of electron transfer is exceedingly fast, and is expected to, conduction speed thinner for development electronic component of new generation or transistor material faster.Because Graphene is in fact a kind of transparent, good conductor, be also applicable to for manufacturing transparent touch screen, tabula rasa or even solar cell.
Summary of the invention
The object of this invention is to provide a kind of Graphene complex copper thick film conductor paste, conduct electricity very well and print thickness little, low-temperature sintering still has excellent electrical property.
Another object of the present invention is to provide the preparation method of above-mentioned electroconductive glue materials.
The technical solution adopted in the present invention is: a kind of Graphene complex copper thick film conductor paste, composed of the following components according to mass percent: conductive phase 60%～80%, glassy phase 0.5%～5%, organic carrier 15%～39.5%, above-mentioned each constituent mass percentage sum is 100%.
Feature of the present invention is also,
Conductive phase is composed of the following components according to mass percent: flake copper 63%～88%, spherical copper powder 10%～35%, Graphene 0.2%～2.0%, and above-mentioned each constituent mass percentage sum is 100%;
Glassy phase is selected bismuth oxide low-melting glass, and it consists of: bismuth oxide 40%～60%, barium monoxide 10～30%, boron oxide 20%～30%, and above-mentioned each constituent mass percentage sum is 100%;
Organic carrier is composed of the following components according to mass percent: ethyl cellulose 2%～10%, terpinol 75%～90%, defoamer 1%～3%, silane coupler 0.1%～2%, ethyl acetate 2%～10%, above-mentioned each constituent mass percentage sum is 100%.
The copper powder that flake copper is 3～25 μ m by particle diameter is made, and the copper powder that spherical copper powder is 0.5～5 μ m by particle diameter is made, and the particle diameter of Graphene is 0.5～3nm.
Flake copper and spherical Copper Powder Surface are all coated with antioxidant, and antioxidant is any one in tributyl phosphate, oleic acid or lactic acid.
In conductive phase, add dispersant, the mass ratio of dispersant and Graphene is 0.2～0.4:1, and dispersant is any one in polyvinylpyrrolidone, sodium carboxymethylcellulose, polyacrylic material.
Defoamer is glycerin polyoxyethylene ether, and silane coupler is gamma-aminopropyl-triethoxy-silane.
Another kind of technical scheme of the present invention is: a kind of preparation method of Graphene complex copper thick film conductor paste, comprises the following steps:
Step 1: getting respectively particle diameter is that 3～25 μ m copper powders and particle diameter are the copper powder of 0.5～5 μ m, with pickling, washing, ethanol, wash successively, then add respectively antioxidant to stir, temperature in 90 ℃～100 ℃ in ammonia or nitrogen atmosphere is dried 2～3h, obtains being respectively coated with the copper powder of antioxidant; By the particle diameter that is coated with antioxidant, be that 3～25 μ m copper powders grindings obtain flake copper, the particle diameter that is coated with antioxidant is that the copper powder of 0.5～5 μ m is spherical copper powder;
Step 2: take respectively each raw material of conductive phase according to mass percent: the Graphene 0.2%～2.0% that flake copper 63%～88%, spherical copper powder 10%～35%, particle diameter are 0.5～3nm, above-mentioned each constituent mass percentage sum is 100%;
According to mass percent, take respectively each raw material of bismuth oxide low-melting glass: bismuth oxide 40%～60%, barium monoxide 10～30%, boron oxide 20%～30%, above-mentioned each constituent mass percentage sum is 100%;
According to mass percent, take respectively each raw material of organic carrier: ethyl cellulose 2%～10%, terpinol 75%～90%, defoamer 1%～3%, silane coupler 0.1%～2%, ethyl acetate 2%～10%, above-mentioned each constituent mass percentage sum is 100%;
Step 3: the flake copper that step 2 is taken, spherical copper powder, Graphene mix, and obtain conductive phase;
The bismuth oxide that step 2 is taken, barium monoxide, boron oxide mix, and obtain bismuth oxide low-melting glass;
The ethyl cellulose that step 2 is taken, terpinol, defoamer, silane coupler and ethyl acetate mix under the temperature conditions of 55～65 ℃, obtain organic carrier;
Step 4: take respectively the following raw material that step 3 obtains according to mass percent: conductive phase 60%～80%, bismuth oxide low-melting glass 0.5%～5%, organic carrier 15%～39.5%, above-mentioned each constituent mass percentage sum is 100%, above-mentioned each component is mixed, be heated to 35～40 ℃, stir, obtain.
Feature of the present invention is also,
In step 1, the watery hydrochloric acid that volumetric concentration is 8～13% is used in pickling; Antioxidant is any one in tributyl phosphate, oleic acid or lactic acid, and the consumption of antioxidant is 1～1.5 times of copper powder volume.
In the conductive phase of step 2, add dispersant, the mass ratio of dispersant and Graphene is 0.2～0.4:1, and dispersant is any one in polyvinylpyrrolidone, sodium carboxymethylcellulose, polyacrylic material.
In step 2, defoamer is glycerin polyoxyethylene ether, and silane coupler is gamma-aminopropyl-triethoxy-silane.
The invention has the beneficial effects as follows: a kind of Graphene complex copper of the present invention thick film conductor paste; the Graphene that adds electric conductivity excellence improves the electric conductivity of slurry; utilize bismuth oxide low-melting glass; even sintering also shows the conductive thick film slurry of excellent electrical property and adhesion under formation low temperature; conduct electricity very well and print thickness little; can be effectively applied to form the electric conducting material of various products; slurry configuration technique is simple; easy to operate; good conductivity; even particle size distribution, is easy to apply, and is suitable for enterprise scale and produces.
Embodiment
Below in conjunction with embodiment, the present invention is described in detail.
A kind of Graphene complex copper of the present invention thick film conductor paste, composed of the following components according to mass percent: conductive phase 60%～80%, glassy phase 0.5%～5%, organic carrier 15%～39.5%, above-mentioned each constituent mass percentage sum is 100%;
Wherein, conductive phase is composed of the following components according to mass percent: the graphene powder 0.2%～2.0% that flake copper 63%～88%, spherical copper powder 10%～35%, particle diameter are 0.5～3nm, and above-mentioned each constituent mass percentage sum is 100%; Wherein, the copper powder that flake copper is 3～25 μ m by particle diameter is made, the copper powder that spherical copper powder is 0.5～5 μ m by particle diameter is made, and flake copper and spherical Copper Powder Surface are all coated with antioxidant, and antioxidant is any one in tributyl phosphate, oleic acid or lactic acid; In conductive phase, can also add dispersant, the mass ratio of dispersant and Graphene is 0.2～0.4:1, and dispersant is any one in polyvinylpyrrolidone, sodium carboxymethylcellulose, polyacrylic acid;
Glassy phase is selected bismuth oxide low-melting glass, and it consists of: bismuth oxide 40%～60%, barium monoxide 10～30%, boron oxide 20%～30%, and above-mentioned each constituent mass percentage sum is 100%;
Organic carrier is composed of the following components according to mass percent: ethyl cellulose 2%～10%, terpinol 75%～90%, defoamer 1%～3%, silane coupler 0.1%～2%, ethyl acetate 2%～10%, above-mentioned each constituent mass percentage sum is 100%, wherein, defoamer is glycerin polyoxyethylene ether (GP-330), and silane coupler is gamma-aminopropyl-triethoxy-silane (KH-550).
The preparation method of above-mentioned electrocondution slurry, comprises the following steps:
Step 1: getting respectively particle diameter is that 3～25 μ m copper powders and particle diameter are the copper powder of 0.5～5 μ m, with the watery hydrochloric acid that volumetric concentration is 8～13%, wash successively, washing, ethanol is washed, then add respectively the antioxidant of 1～1.5 times of copper powder volume to stir, antioxidant is tributyl phosphate, any one in oleic acid or lactic acid, temperature in 90 ℃～100 ℃ in ammonia or nitrogen atmosphere is dried 2～3h, obtain being respectively coated with the copper powder of antioxidant, by the particle diameter that is coated with antioxidant, be that 3～25 μ m copper powders grindings obtain flake copper, the particle diameter that is coated with antioxidant is that the copper powder of 0.5～5 μ m is spherical copper powder,
Step 2: take respectively each raw material of conductive phase according to mass percent: the graphene powder 0.2%～2.0% that flake copper 63%～88%, spherical copper powder 10%～35%, particle diameter are 0.5～3nm, above-mentioned each constituent mass percentage sum is 100%; In conductive phase, can also add dispersant, the mass ratio of dispersant and Graphene is 0.2～0.4:1, and dispersant is any one in polyvinylpyrrolidone, sodium carboxymethylcellulose, polyacrylic acid;
According to mass percent, take respectively each raw material of bismuth oxide low-melting glass: bismuth oxide 40%～60%, barium monoxide 10～30%, boron oxide 20%～30%, above-mentioned each constituent mass percentage sum is 100%;
According to mass percent, take respectively each raw material of organic carrier: ethyl cellulose 2%～10%, terpinol 75%～90%, defoamer 1%～3%, silane coupler 0.1%～2%, ethyl acetate 2%～10%, above-mentioned each constituent mass percentage sum is 100%; Wherein, defoamer is glycerin polyoxyethylene ether, and silane coupler is gamma-aminopropyl-triethoxy-silane;
Step 3: the flake copper that step 2 is taken, spherical copper powder, Graphene mix, and obtain conductive phase;
The bismuth oxide that step 2 is taken, barium monoxide, boron oxide mix, and obtain bismuth oxide low-melting glass;
The ethyl cellulose that step 2 is taken, terpinol, defoamer, silane coupler and ethyl acetate mix under the temperature conditions of 55～65 ℃, obtain organic carrier;
Step 4: take respectively the following raw material that step 3 obtains according to mass percent: conductive phase 60%～80%, bismuth oxide low-melting glass 0.5%～5%, organic carrier 15%～39.5%, above-mentioned each constituent mass percentage sum is 100%, above-mentioned each component is mixed, be heated to 35～40 ℃, stir, obtain.
At flake copper and the coated antioxidant of spherical Copper Powder Surface, can prevent that Copper Powder Surface is again oxidized, thereby affect electric conductivity; In conductive phase, add polyethylene of dispersing agent pyrrolidones, sodium carboxymethylcellulose, polyacrylic material, can strengthen Graphene and mix with the good of copper powder.
Glassy phase is selected bismuth oxide low-melting glass, can when sintering, melting soften cementation mutually, and average grain diameter is less than 10 μ m, can also add as required zinc oxide, aluminium oxide to regulate the coefficient of expansion of glass and the transition temperature of glass in glassy phase.
Electrocondution slurry prepared by the present invention can be applicable in thin film switch, circuit and board production, even and electrocondution slurry sintering at the temperature of 200 ℃ also shows excellent electrical property and adhesion, overcome in sintering process high temperature and caused conductive phase oxidized and affect electric conductivity.
The invention has the beneficial effects as follows:
(1) in the present invention, conductive phase is comprised of flake copper, spherical copper powder and nano level graphene powder, spherical can contact well sheet and spherical and nano level, conductive phase contact area has expanded, spherical copper powder and nanoscale graphene powder have polymolecularity, the space between flake copper particle be can effectively be filled in, thereby filling rate, uniformity and the printing quality of slurry improved;
(2) in the present invention, Graphene has excellent electric conductivity and large specific area, in conductive phase, only need to add few part and just can improve significantly slurry electric conductivity, but also reduced the solid content in electrocondution slurry, reduced coating layer thickness, made coating to thinner Conducting Films with High Performance future development;
(3) in the present invention, glassy phase is selected bismuth oxide low-melting glass,, containing human body and environment being had to lead, cadmium, the chromium element of harm, can not substitute the leaded low-melting glass using in current electric slurry used; And make slurry there is sintering at the temperature of 200 ℃ and also show excellent electrical property and adhesion, overcome in sintering process high temperature and caused conductive phase oxidized and affect electric conductivity;
(4) electrocondution slurry configuration technique of the present invention is simple, easy to operate, good conductivity, and even particle size distribution, is easy to apply, and is easy to realize large-scale industrial and produces, and can be applicable in thin film switch, circuit and board production;
(5) electrocondution slurry sintered membrane electric property of the present invention, solderability, adhesive force, hardness and chemical stability are good, and while making electronic devices and components, its sintering temperature is very low, is convenient to energy-conservation.
Embodiment 1
Step 1: getting respectively particle diameter is that 3 μ m copper powders and particle diameter are the copper powder of 0.5 μ m, successively with the watery hydrochloric acid that volumetric concentration is 8% wash, washing, absolute ethyl alcohol wash, then add the tributyl phosphate equating with copper powder volume, temperature in 100 ℃ in ammonia atmosphere is dried 2h, the particle diameter that obtains being respectively coated with tributyl phosphate is the copper powder of 3 μ m and 0.5 μ m, the copper powder that is 3 μ m by the particle diameter that is coated with tributyl phosphate grinds and obtains flake copper, and the particle diameter that is coated with tributyl phosphate is that the copper powder of 0.5 μ m is spherical copper powder;
Step 2: take respectively each raw material of conductive phase: the graphene powder 2g that flake copper 63g, spherical copper powder 35g, particle diameter are 0.5nm;
Take respectively each raw material of bismuth oxide low-melting glass: bismuth oxide 40g, barium monoxide 30g, boron oxide 30g;
Take respectively each raw material of organic carrier: ethyl cellulose 2g, terpinol 90g, defoamer (GP-330) 2g, silane coupler (KH-550) 0.1g, ethyl acetate 5.9g;
Step 3: the flake copper that step 2 is taken, spherical copper powder, graphene powder are mixed to get conductive phase;
The bismuth oxide that step 2 is taken, barium monoxide, boron oxide mix, and obtain bismuth oxide low-melting glass;
The ethyl cellulose that step 2 is taken, terpinol, GP-330, KH-550 and ethyl acetate mix under the temperature conditions of 55 ℃, obtain organic carrier;
Step 4: take respectively the following raw material that step 3 obtains according to mass percent: conductive phase 60%, bismuth oxide low-melting glass 0.5%, organic carrier 39.5%, above-mentioned each component is mixed, be heated to 35 ℃, stir, obtain.
Embodiment 2
Step 1: getting respectively particle diameter is that 15 μ m copper powders and particle diameter are the copper powder of 3 μ m, successively with the watery hydrochloric acid that volumetric concentration is 10% wash, washing, absolute ethyl alcohol wash, then the oleic acid that adds 1.5 times of copper powder volume summations, temperature in 90 ℃ in nitrogen atmosphere is dried 3h, the particle diameter that obtains being respectively coated with oleic acid is that 15 μ m and particle diameter are the copper powder of 3 μ m, the copper powder that is 15 μ m by the particle diameter that is coated with oleic acid grinds and obtains flake copper, and the particle diameter that is coated with oleic acid is that the copper powder of 3 μ m is spherical copper powder;
Step 2: take respectively each raw material of conductive phase: graphene powder 2g, polyvinylpyrrolidone 0.4g that flake copper 88g, spherical copper powder 10g, particle diameter are 0.5nm;
Take respectively each raw material of bismuth oxide low-melting glass: bismuth oxide 60g, barium monoxide 20g, boron oxide 20g;
Take respectively each raw material of organic carrier: ethyl cellulose 10g, terpinol 75g, defoamer (GP-330) 3g, silane coupler (KH-550) 2g, ethyl acetate 10g;
Step 3: the flake copper that step 2 is taken, spherical copper powder, graphene powder mix, and obtain conductive phase;
The bismuth oxide that step 2 is taken, barium monoxide, boron oxide mix, and obtain bismuth oxide low-melting glass;
The ethyl cellulose that step 2 is taken, terpinol, GP-330, KH-550 and ethyl acetate mix under the temperature conditions of 60 ℃, obtain organic carrier;
Step 4: take respectively the following raw material that step 3 obtains according to mass percent: conductive phase 80%, bismuth oxide low-melting glass 5%, organic carrier 15%, above-mentioned each component is mixed, be heated to 40 ℃, stir, obtain.
Embodiment 3
Step 1: getting respectively particle diameter is that 25 μ m copper powders and particle diameter are the copper powder of 5 μ m, successively with the watery hydrochloric acid that volumetric concentration is 13% wash, washing, absolute ethyl alcohol wash, then the lactic acid that adds 1.2 times of copper powder volume summations, temperature in 95 ℃ in nitrogen atmosphere is dried 2.5h, the particle diameter that obtains being respectively coated with lactic acid is that 25 μ m and particle diameter are the copper powder of 5 μ m, the copper powder that is 25 μ m by the particle diameter that is coated with lactic acid grinds and obtains flake copper, and the particle diameter that is coated with lactic acid is that the copper powder of 5 μ m is spherical copper powder;
Step 2: take respectively each raw material of conductive phase: graphene powder 0.2g, sodium carboxymethylcellulose 0.08g that flake copper 77g, spherical copper powder 22.8g, particle diameter are 3nm;
Take respectively each raw material of bismuth oxide low-melting glass: bismuth oxide 60g, barium monoxide 10g, boron oxide 30g;
Take respectively each raw material of organic carrier: ethyl cellulose 8g, terpinol 88g, defoamer (GP-330) 1g, silane coupler (KH-550) 1g, ethyl acetate 2g;
Step 3: the flake copper that step 2 is taken, spherical copper powder, graphene powder mix, and obtain conductive phase;
The bismuth oxide that step 2 is taken, barium monoxide, boron oxide mix, and obtain bismuth oxide low-melting glass;
The ethyl cellulose that step 2 is taken, terpinol, GP-330, KH-550 and ethyl acetate mix under the temperature conditions of 65 ℃, obtain organic carrier;
Step 4: take respectively the following raw material that step 3 obtains according to mass percent: conductive phase 77%, bismuth oxide low-melting glass 3%, organic carrier 20%, above-mentioned each component is mixed, be heated to 38 ℃, stir, obtain.
Embodiment 4
Step 1: getting respectively particle diameter is that 10 μ m copper powders and particle diameter are the copper powder of 2 μ m, successively with the watery hydrochloric acid that volumetric concentration is 12% wash, washing, absolute ethyl alcohol wash, then the lactic acid that adds 1.4 times of flake copper and spherical copper powder volume summations, temperature in 98 ℃ in nitrogen atmosphere is dried 2.5h, the particle diameter that obtains being respectively coated with lactic acid is that 10 μ m and particle diameter are the copper powder of 2 μ m, the copper powder that is 10 μ m by the particle diameter that is coated with lactic acid grinds and obtains flake copper, and the particle diameter that is coated with lactic acid is that the copper powder of 2 μ m is spherical copper powder;
Step 2: take respectively each raw material of conductive phase: graphene powder 1g, polyacrylic acid 0.3g that flake copper 70g, spherical copper powder 29g, particle diameter are 1nm;
Take respectively each raw material of bismuth oxide low-melting glass: bismuth oxide 50g, barium monoxide 30g, boron oxide 20g;
Take respectively each raw material of organic carrier: ethyl cellulose 5g, terpinol 85g, defoamer (GP-330) 2g, silane coupler (KH-550) 2g, ethyl acetate 6g;
Step 3: the flake copper that step 2 is taken, spherical copper powder, graphene powder mix, and obtain conductive phase;
The bismuth oxide that step 2 is taken, barium monoxide, boron oxide mix, and obtain bismuth oxide low-melting glass;
The ethyl cellulose that step 2 is taken, terpinol, GP-330, KH-550 and ethyl acetate mix under the temperature conditions of 63 ℃, obtain organic carrier;
Step 4: take respectively the following raw material that step 3 obtains according to mass percent: conductive phase 65%, bismuth oxide low-melting glass 5%, organic carrier 30%, above-mentioned each component is mixed, be heated to 40 ℃, stir, obtain.
At present, the resistance of copper slurry is at 30～70n Ω, and its print thickness is between 20～30 μ m scopes, and the conductivity of the Graphene complex copper thick film conductor paste that the present invention makes promotes more than 20%, and print thickness can reduce by 20～30%.
Claims (10)
1. a Graphene complex copper thick film conductor paste, it is characterized in that, composed of the following components according to mass percent: conductive phase 60%～80%, glassy phase 0.5%～5%, organic carrier 15%～39.5%, above-mentioned each constituent mass percentage sum is 100%.
2. a kind of Graphene complex copper thick film conductor paste as claimed in claim 1, it is characterized in that, described conductive phase is composed of the following components according to mass percent: flake copper 63%～88%, spherical copper powder 10%～35%, Graphene 0.2%～2.0%, and above-mentioned each constituent mass percentage sum is 100%;
Described glassy phase is selected bismuth oxide low-melting glass, and it consists of: bismuth oxide 40%～60%, barium monoxide 10～30%, boron oxide 20%～30%, and above-mentioned each constituent mass percentage sum is 100%;
Described organic carrier is composed of the following components according to mass percent: ethyl cellulose 2%～10%, terpinol 75%～90%, defoamer 1%～3%, silane coupler 0.1%～2%, ethyl acetate 2%～10%, above-mentioned each constituent mass percentage sum is 100%.
3. a kind of Graphene complex copper thick film conductor paste as claimed in claim 2, is characterized in that, the copper powder that described flake copper is 3～25 μ m by particle diameter is made, and the copper powder that spherical copper powder is 0.5～5 μ m by particle diameter is made, and the particle diameter of Graphene is 0.5～3nm.
4. a kind of Graphene complex copper thick film conductor paste as claimed in claim 2, is characterized in that, described flake copper and described spherical Copper Powder Surface are all coated with antioxidant, and described antioxidant is any one in tributyl phosphate, oleic acid or lactic acid.
5. a kind of Graphene complex copper thick film conductor paste as claimed in claim 2, it is characterized in that, in described conductive phase, add dispersant, the mass ratio of dispersant and Graphene is 0.2～0.4:1, and described dispersant is any one in polyvinylpyrrolidone, sodium carboxymethylcellulose, polyacrylic material.
6. a kind of Graphene complex copper thick film conductor paste as claimed in claim 2, is characterized in that, wherein, described defoamer is glycerin polyoxyethylene ether, and silane coupler is gamma-aminopropyl-triethoxy-silane.
7. a preparation method for Graphene complex copper thick film conductor paste, is characterized in that, comprises the following steps:
Step 1: getting respectively particle diameter is that 3～25 μ m copper powders and particle diameter are the copper powder of 0.5～5 μ m, with pickling, washing, ethanol, wash successively, then add respectively antioxidant to stir, temperature in 90 ℃～100 ℃ in ammonia or nitrogen atmosphere is dried 2～3h, obtains being respectively coated with the copper powder of antioxidant; By the particle diameter that is coated with antioxidant, be that 3～25 μ m copper powders grindings obtain flake copper, the particle diameter that is coated with antioxidant is that the copper powder of 0.5～5 μ m is spherical copper powder;
Step 2: take respectively each raw material of conductive phase according to mass percent: the Graphene 0.2%～2.0% that flake copper 63%～88%, spherical copper powder 10%～35%, particle diameter are 0.5～3nm, above-mentioned each constituent mass percentage sum is 100%;
According to mass percent, take respectively each raw material of bismuth oxide low-melting glass: bismuth oxide 40%～60%, barium monoxide 10～30%, boron oxide 20%～30%, above-mentioned each constituent mass percentage sum is 100%;
According to mass percent, take respectively each raw material of organic carrier: ethyl cellulose 2%～10%, terpinol 75%～90%, defoamer 1%～3%, silane coupler 0.1%～2%, ethyl acetate 2%～10%, above-mentioned each constituent mass percentage sum is 100%;
Step 3: the flake copper that described step 2 is taken, spherical copper powder, Graphene mix, and obtain conductive phase;
The bismuth oxide that described step 2 is taken, barium monoxide, boron oxide mix, and obtain bismuth oxide low-melting glass;
The ethyl cellulose that described step 2 is taken, terpinol, defoamer, silane coupler and ethyl acetate mix under the temperature conditions of 55～65 ℃, obtain organic carrier;
Step 4: take respectively the following raw material that described step 3 obtains according to mass percent: conductive phase 60%～80%, bismuth oxide low-melting glass 0.5%～5%, organic carrier 15%～39.5%, above-mentioned each constituent mass percentage sum is 100%, above-mentioned each component is mixed, be heated to 35～40 ℃, stir, obtain.
8. the preparation method of a kind of Graphene complex copper thick film conductor paste as claimed in claim 7, is characterized in that, in described step 1, the watery hydrochloric acid that volumetric concentration is 8～13% is used in pickling; Described antioxidant is any one in tributyl phosphate, oleic acid or lactic acid, and the consumption of antioxidant is 1～1.5 times of copper powder volume.
9. the preparation method of a kind of Graphene complex copper thick film conductor paste as claimed in claim 7, it is characterized in that, in the conductive phase of described step 2, add dispersant, the mass ratio of dispersant and Graphene is 0.2～0.4:1, and described dispersant is any one in polyvinylpyrrolidone, sodium carboxymethylcellulose, polyacrylic material.
10. the preparation method of a kind of Graphene complex copper thick film conductor paste as claimed in claim 7, is characterized in that, in described step 2, defoamer is glycerin polyoxyethylene ether, and silane coupler is gamma-aminopropyl-triethoxy-silane.
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| CN105469856A (en) * | 2015-12-24 | 2016-04-06 | 东莞佐佑电子科技有限公司 | Low-temperature thick film circuit paste and preparation method therefor |
| CN105682346A (en) * | 2016-02-03 | 2016-06-15 | 武汉华尚绿能科技股份有限公司 | Manufacturing method for high-conduction transparent glass-based circuit board |
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| CN108231241A (en) * | 2018-01-19 | 2018-06-29 | 林荣铨 | The preparation and its application of a kind of medium temperature graphene/copper composite conducting slurry |
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| CN109852835A (en) * | 2019-01-23 | 2019-06-07 | 南京工业大学 | Preparation method of graphene/copper nanocomposite |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105469856A (en) * | 2015-12-24 | 2016-04-06 | 东莞佐佑电子科技有限公司 | Low-temperature thick film circuit paste and preparation method therefor |
| CN105682346A (en) * | 2016-02-03 | 2016-06-15 | 武汉华尚绿能科技股份有限公司 | Manufacturing method for high-conduction transparent glass-based circuit board |
| CN105761769A (en) * | 2016-04-23 | 2016-07-13 | 上海大学 | Method for preparing tungstenic anti-radiation shielding film composite material through spin coating method |
| US10593438B2 (en) * | 2016-05-16 | 2020-03-17 | Nantong T-Sun New Energy Co., Ltd. | Solar cell front side silver paste doped with modified graphene and preparation method thereof |
| US20180226172A1 (en) * | 2016-05-16 | 2018-08-09 | Nantong T-Sun New Energy Co.,Ltd. | Solar cell front side silver paste doped with modified grapheme and preparation method thereof |
| CN106782885B (en) * | 2016-12-19 | 2018-07-03 | 西安工程大学 | A kind of preparation method of nano silver wire-copper staple fiber-copper composite electron slurry |
| CN106782885A (en) * | 2016-12-19 | 2017-05-31 | 西安工程大学 | A kind of preparation method of nano silver wire copper chopped fiber copper composite electron slurry |
| CN107768021A (en) * | 2017-09-25 | 2018-03-06 | 江苏时瑞电子科技有限公司 | A kind of preparation method of composite conducting slurry |
| CN107731341A (en) * | 2017-09-25 | 2018-02-23 | 江苏时瑞电子科技有限公司 | A kind of negative tempperature coefficient thermistor compound copper electrode paste and preparation method thereof |
| CN107591219A (en) * | 2017-09-25 | 2018-01-16 | 江苏时瑞电子科技有限公司 | A kind of electrocondution slurry of graphene-containing and preparation method thereof |
| CN108231241A (en) * | 2018-01-19 | 2018-06-29 | 林荣铨 | The preparation and its application of a kind of medium temperature graphene/copper composite conducting slurry |
| CN109004227A (en) * | 2018-08-02 | 2018-12-14 | 无锡泰科纳米新材料有限公司 | A kind of lithium ion battery graphene conductive slurry and preparation method thereof |
| CN109004227B (en) * | 2018-08-02 | 2020-07-14 | 无锡泰科纳米新材料有限公司 | Graphene conductive slurry for lithium ion battery and preparation method thereof |
| CN109852835A (en) * | 2019-01-23 | 2019-06-07 | 南京工业大学 | Preparation method of graphene/copper nanocomposite |
| CN111393910A (en) * | 2020-05-11 | 2020-07-10 | 南昌航空大学 | Composite nano-copper conductive ink, preparation method thereof and conductive device |
| CN114639506A (en) * | 2022-05-20 | 2022-06-17 | 西安宏星电子浆料科技股份有限公司 | Low-temperature fast-sintering conductive copper paste and preparation method thereof |
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